EP0699695A2 - Procédé de préparation de copolyacétals - Google Patents

Procédé de préparation de copolyacétals Download PDF

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Publication number
EP0699695A2
EP0699695A2 EP95113209A EP95113209A EP0699695A2 EP 0699695 A2 EP0699695 A2 EP 0699695A2 EP 95113209 A EP95113209 A EP 95113209A EP 95113209 A EP95113209 A EP 95113209A EP 0699695 A2 EP0699695 A2 EP 0699695A2
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EP
European Patent Office
Prior art keywords
polymerization
product
extraction
residual monomers
stabilization
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP95113209A
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German (de)
English (en)
Other versions
EP0699695B1 (fr
EP0699695A3 (fr
Inventor
Dietrich Dr. Fleischer
Michael Dr. Hoffmockel
Karl-Friedrich Dr. Mück
Günter Dr. Sextro
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Ticona GmbH
Original Assignee
Hoechst AG
Ticona GmbH
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Publication date
Application filed by Hoechst AG, Ticona GmbH filed Critical Hoechst AG
Publication of EP0699695A2 publication Critical patent/EP0699695A2/fr
Publication of EP0699695A3 publication Critical patent/EP0699695A3/fr
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Publication of EP0699695B1 publication Critical patent/EP0699695B1/fr
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Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
    • C08G2/18—Copolymerisation of aldehydes or ketones
    • C08G2/24—Copolymerisation of aldehydes or ketones with acetals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
    • C08G2/10—Polymerisation of cyclic oligomers of formaldehyde
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
    • C08G2/28—Post-polymerisation treatments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating

Definitions

  • the invention relates to a process for the preparation and end group stabilization of polyacetal copolymers in a homogeneous phase, and their workup.
  • a common feature of these processes is a phase transition from gaseous or liquid monomers to the partially crystalline solid polymer that occurs during the polymerization. This leads to problems in the dissipation of the heat of polymerization and crystallization released and causes losses in sales as a result.
  • European patent EP-B-0 080 656 describes a process for the continuous bulk polymerization of trioxane in a homogeneous, liquid phase at temperatures above 135 ° C.
  • the advantages of this method include called: easy handling of the process, low energy consumption and polymers with constant product quality.
  • the invention describes a process for the preparation and simultaneous end group stabilization of polyacetal copolymers in a homogeneous phase and their workup, in which cyclic formaldehyde oligomers, preferably trioxane, are copolymerized with cyclic acetals in the presence of an initiator in a polymerization reactor and, after the polymerization step, the initiator is deactivated by adding basic substances is, the unstable chain ends are degraded in the presence of residual monomers to 0.01% to 1%, preferably 0.02% to 0.5%, in particular 0.05% to 0.3% and the product at the reactor outlet by relaxation in a granulating device, preferably in a liquid ring or sub-liquid granulating device, which are each operated with water, alcohols with up to three carbon atoms, preferably methanol, or mixtures thereof, lose a large part of the residual monomers and the remaining residual monomers and in the Product-dissolved impurities are removed by extraction with solvents such as water, alcohols with up to
  • the polymerization and the degradation of the unstable chain ends is preferably carried out in a tubular reactor.
  • the method is based on the German patent applications P 43 27 245.2 and P 44 23 617.4 described above, to which reference is hereby made.
  • the starting monomer for the copolymerization according to the invention is generally trioxane. It is crucial for the successful course of the process that the necessary chain end degradation immediately follows the polymerization and in the presence of residual monomers, i.e. unreacted monomers.
  • Suitable comonomers for the polymerization of, for example, trioxane are cyclic acetals, such as dioxolane, diethylene glycol or triethylene glycol formal, butanediol formal or linear polyacetals, for example polydioxolane or polyethylene glycol formal.
  • the proportions of the comonomers, or mixtures thereof, are 0.5 to 50 percent by mass, preferably 1 to 30 percent by mass, in particular 2 to 10 percent by mass.
  • the comonomers can be added either as a mixture with the main monomer or in the form of a reactive prepolymer. It is also feasible to feed the comonomer or comonomers into the polymer melt after homopolymerization of the main monomer.
  • the corresponding comonomer (s) are then randomly incorporated into the polymer chain by transacetalization reactions.
  • the required residence time of the reaction mixture in the polymerization-active state for this reaction is in the range from 0.1 to 10 minutes, preferably 0.3 to 5 minutes, in particular 0.5 to 2 minutes.
  • bifunctional comonomers leads to partially crosslinked or branched products.
  • Suitable initiators are protonic acids such as perchloric acid, perfluoroalkanesulfonic acids, preferably trifluoromethanesulfonic acid and their anhydrides, and also heteropolyacids or isopolyacids (EP-B-0 325 052 and EP-B-0 347 119).
  • the initiators can be used in amounts of 0.005 to 500 ppm.
  • the preferred range is 0.01 to 50 ppm, especially 0.01 to 5 ppm. Since the initiator concentration influences the molar mass to a large extent, it is advisable to dose the initiator in dissolved, diluted form.
  • all compounds which do not influence the polymerization can be used as solvents; cyclic and linear ethers such as oligoglycol dialkyl ethers or their mixtures with aliphatic or cycloaliphatic hydrocarbons, e.g. Cyclohexane; lactones such as butyrolactone are also suitable.
  • the molecular weights of the polymers can be adjusted to the desired values in a known manner by means of regulators.
  • Formal chain monohydric alcohols such as methylal or butylal are primarily suitable as chain transfer agents. Also suitable are the alcohols on which these compounds are based, or water as a regulator, although they cause the formation of unstable chain ends during chain transfer.
  • the amounts usually used are 10 to 5000 ppm, the preferred concentration between 50 and 1000 ppm.
  • the regulators can be metered in a known manner by admixing them with the monomers. However, it is also possible to meter the substances serving as regulators together with the initiator in the same solution or separately.
  • the polymerization reactor is generally one with static mixers designed tubular reactor that is designed to be temperature-controlled and pressure-resistant. By setting temperature control zones, a specific temperature profile can be impressed on the reactor. Along the reactor there are measuring points for pressure and temperature as well as metering points for monomers, initiators, deactivators and other additives.
  • the temperatures and pressures used in the polymerization correspond to the customary values known in practice, as described, for example, in EP-B-0 080 656.
  • the dimensions i.e. Select the diameter and length of the corresponding static mixing elements as a function of viscosity and residence time, with the pressure loss being kept as small as possible.
  • the pressure loss being kept as small as possible.
  • a tubular reactor should be designed in such a way that a narrow residence time spectrum results, which enables equilibrium conversion, in which case minimal side reactions inevitably occur due to the minimized residence time.
  • German patent application P 43 27 246.0 to which reference is hereby made. It is also possible to use other units, for example extruders, for the polymerization and / or for the degradation of the unstable chain ends in the presence of the residual monomers.
  • the residence time to be observed in the polymerization zone is 0.1 to 10 minutes, preferably 0.3 to 5 minutes and in particular 0.5 to 2 minutes.
  • the conversion to be achieved is 60 to 80 percent by mass, based on the monomers used.
  • the molar masses (M w ) of the polyacetals produced are in the range from 50,000 to 300,000 (GPC against polystyrene standard) without using regulators.
  • basic compounds e.g. Salts such as soda or disodium hydrogen phosphate and aliphatic or aromatic primary, secondary or tertiary amines are used; volatile tertiary amines, e.g. Triethylamine.
  • the concentrations of the alkaline agents range from 0.001 to 3.0% by mass, based on the amount of polymer, the range from 0.02 to 2.0% by mass and in particular from 0.05 to 1.0% by mass being preferred.
  • the temperature to be used in the second process step in the deactivation zone, in which the unstable chain ends are also degraded is 150 ° C. to 250 ° C., preferably 170 ° C. to 200 ° C. It has proven advantageous for the rate of degradation to remain 20 to 30 ° C. above the polymerization temperature.
  • the pressure range to be observed ranges from 20 to 200 bar, preferably from 20 to 50 bar.
  • the residence time to be set in the deactivator and stabilization zone is 0.2 to 15 minutes, preferably 1 to 15 minutes, in particular 2 to 10 mins.
  • a polymerization zone P and a deactivation zone D are present in a polymerization reactor R.
  • the polymer feed zone P is preceded by the monomer feed 1 and the initiator feed 2.
  • the deactivator metering 3 takes place at the end of the polymerization zone P and in front of the deactivation zone D.
  • Appropriate reaction in the polymerization zone P and the deactivation zone D gives a stream at the reactor outlet 4 consisting of a melt of a polymer with a proportion of unstable chain ends of 0.01 % to 1%, preferably 0.02% to 0.5%, in particular 0.05% to 0.3% and residual monomers and deactivators and, if appropriate, solvents.
  • the suspension obtained from the liquid ring granulating device G is separated into liquid and solid in the collecting container B. If necessary, can the product is also subjected to wet grinding beforehand in order to promote the removal of the residual monomers, but this is not shown in the figure.
  • the process material reaches the separating device Z1 via a line 5. In principle, all the usual equipment and machines such as sieves, filters, hydrocyclones can be used for separation; centrifuges have proven to be particularly suitable.
  • the liquid is partly returned as cooling liquid 6 to the liquid ring granulation G and partly fed to a workup 7 in a known manner for the recovery of the residual monomers and the solvents.
  • Solid with an adhering liquid is fed to an extraction E via a line 8.
  • Suitable extractants are water and alcohols with up to three carbon atoms, preferably methanol, and mixtures thereof.
  • the products produced by the above polymerization process contain a proportion of formaldehyde oligomers which cannot be removed from the polymer by degassing. It has been shown that these formaldehyde oligomers can be extracted from the polymer under mild conditions. To accelerate the process, it is possible to grind the product further before the extraction or directly after the liquid ring granulation G. In order to ensure rapid extraction, it is desirable to keep the particle size in the range from 50 to 2000 ⁇ m, preferably 100 to 1500 ⁇ m, in particular 200 to 1000 ⁇ m.
  • Suitable extractants are water, alcohols with up to three carbon atoms, preferably methanol, or mixtures thereof.
  • the extractant is also suitable to be used as cooling liquid after the liquid ring granulation G in the collecting container B and can therefore partly after it has reached the separating device Z2 via a line 9, from this via a line 11 into the collecting container B or returned to extraction E via a line 10 will.
  • the temperature to be used for the extraction is in the range from 30 to 130 ° C., preferably from 35 ° C. to 100 ° C., in particular from 40 to 70 ° C.
  • the times required for the extraction are 1 to 60, preferably 5 to 45, in particular 10 to 30 minutes.
  • the extraction enables solids contents of up to 30 percent by mass, preferably up to 20 percent by mass, to be achieved.
  • the material to be separated is then dried in a dryer T by conventional methods and the condensate from the dryer T is returned to the extraction E via line 15.
  • the powder obtained can be in a known manner with the addition of stabilizers 16 and possibly other additives in an extruder 14. It is advantageous if the polymer powder has a high bulk density, since this ensures optimal operation of the extruder 14.
  • the process according to the invention was carried out in a tubular reactor.
  • the reaction conditions were as follows: The continuous copolymerization with a throughput of 3 kg / h of 97 parts by weight of trioxane and 3 parts by weight of dioxolane, to which 450 ppm of methylal had been added, was initiated with 0.2 ppm of trifluoromethanesulfonic acid, dissolved in diethylene glycol dimethyl ether. The polymerization at 155 ° C. was terminated after 1.8 minutes with 0.3% triethylamine and 4% water and the unstable chain ends were broken down at 155 ° C. in 15 minutes. A product with an unstable chain end fraction of 0.3% was obtained.
  • the product from Comparative Example 1 was washed with methanol in order to remove the adhering residual monomers. The product was then dried to constant weight at 80 ° C. in a drying cabinet under reduced pressure. The product obtained in this way was ground to an average grain diameter of 400 ⁇ m and used for the following extraction experiments.
  • Example 9 The extractable formaldehyde content was drastically reduced under all extraction conditions.
  • Example 3 gave a particularly good result.
  • Example 8 also found a very low extractable formaldehyde content under particularly mild conditions. These extraction conditions were recreated in five batches in the pilot plant boiler and 25 kg of product were produced, stabilized and granulated. In contrast to a non-extracted product, which was degassed in an extruder at a reduced pressure of 50 mbar and had an extractable formaldehyde content of 39 ⁇ g / cm2 (comparative example 2), this product was found to be produced after injection molding after 1200 rounds at a cylinder temperature of 250 ° C and mold temperature of 80 ° C no mold coating (Example 9).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polyethers (AREA)
  • Polyesters Or Polycarbonates (AREA)
EP95113209A 1994-09-05 1995-08-23 Procédé de préparation de copolyacétals Expired - Lifetime EP0699695B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4431575 1994-09-05
DE4431575A DE4431575A1 (de) 1994-09-05 1994-09-05 Verfahren zur Herstellung von Polyacetalcopolymeren

Publications (3)

Publication Number Publication Date
EP0699695A2 true EP0699695A2 (fr) 1996-03-06
EP0699695A3 EP0699695A3 (fr) 1997-10-01
EP0699695B1 EP0699695B1 (fr) 2002-07-31

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Application Number Title Priority Date Filing Date
EP95113209A Expired - Lifetime EP0699695B1 (fr) 1994-09-05 1995-08-23 Procédé de préparation de copolyacétals

Country Status (10)

Country Link
US (1) US5587449A (fr)
EP (1) EP0699695B1 (fr)
JP (1) JP3369365B2 (fr)
KR (1) KR100360288B1 (fr)
CN (1) CN1131163A (fr)
BR (1) BR9503924A (fr)
CA (1) CA2157456A1 (fr)
DE (2) DE4431575A1 (fr)
ES (1) ES2180598T3 (fr)
TW (1) TW376392B (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5886139A (en) * 1996-04-12 1999-03-23 Polyplastics Co., Ltd. Process for producing polyacetal copolymer
WO2006105970A1 (fr) * 2005-04-08 2006-10-12 Ticona Gmbh Procede pour produire des homopolymeres et des copolymeres de polyoxymethylene et dispositif associe
WO2006120218A1 (fr) * 2005-05-11 2006-11-16 Basf Aktiengesellschaft Procede ameliore d'extraction de monomeres residuels a partir de polyoxymethylenes
WO2013020830A2 (fr) 2011-08-11 2013-02-14 Basf Se Procédé de traitement de polyoxyméthylène brut particulaire

Families Citing this family (27)

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JP3269776B2 (ja) * 1996-09-30 2002-04-02 ポリプラスチックス株式会社 安定化オキシメチレン共重合体の製造方法
US5962623A (en) * 1998-09-08 1999-10-05 Ticona Gmbh Process for the preparation of polyacetal copolymers
JP4605904B2 (ja) * 1998-09-24 2011-01-05 旭化成ケミカルズ株式会社 ポリオキシメチレンコポリマーおよびその組成物
KR20020047182A (ko) * 1999-09-24 2002-06-21 로버트 비. 스틸레스 추출가능물을 제거하는 데 사용된 용제의 정제 및 재활용방법
DE10006037A1 (de) * 2000-02-10 2001-08-16 Basf Ag Verfahren zur Herstellung von Polyoxymethylenen
DE10251332B4 (de) * 2002-11-05 2006-07-27 Ticona Gmbh Polyoxymethylen-Copolymere, deren Herstellung und Verwendung
EP1578591A1 (fr) * 2002-12-23 2005-09-28 Dow Global Technologies Inc. Method of smc molding
US20070073007A1 (en) * 2003-11-07 2007-03-29 Hatsuhiko Harashina Polyacetal resin composition and molded article thereof
DE102004025366A1 (de) * 2004-05-19 2005-12-15 Basf Ag Verfahren zur Enfernung von Restmonomeren aus Polyoxymethylenen
DE102004057867A1 (de) * 2004-11-30 2006-06-01 Basf Ag Verfahren zur Herstellung von Polyoxymethylenen
US20060252912A1 (en) * 2005-04-15 2006-11-09 Ticona Gmbh Process for preparing polyoxymethylene homo- and copolymers and apparatus suitable for this purpose
DE102005062327A1 (de) * 2005-12-24 2007-06-28 Ticona Gmbh Verfahren zur Herstellung von Oxymethylen-Polymeren in homogener Phase und Verwendung
US7812110B2 (en) * 2005-12-24 2010-10-12 Ticona Gmbh Process for preparation of oxymethylene polymers, selected polymers, and their use
US7943726B2 (en) * 2005-12-24 2011-05-17 Ticona Gmbh Process for preparation of oxymethylene polymers in a homogeneous phase, and use
WO2008143286A1 (fr) * 2007-05-21 2008-11-27 Kuraray Co., Ltd. Poudre poreuse d'acétal polyvinylique réticulable, son procédé de fabrication et son utilisation
DE102007057189A1 (de) * 2007-11-28 2009-06-04 Automatik Plastics Machinery Gmbh Verfahren und Vorrichtung zur Herstellung von Polyamid
DE102008018967A1 (de) * 2008-04-16 2009-10-22 Ticona Gmbh Oxymethylenpolymere, Verfahren zu deren Herstellung und deren Verwendung
DE102008018966A1 (de) * 2008-04-16 2009-10-22 Ticona Gmbh Verfahren zur Herstellung von Oxymethylen-Polymeren und dafür geeignete Vorrichtung
KR100893693B1 (ko) * 2008-10-27 2009-04-17 원진중공업 주식회사 고 순도의 트리옥산 및 폴리아세탈의 제조방법
US8840976B2 (en) 2010-10-14 2014-09-23 Ticona Llc VOC or compressed gas containment device made from a polyoxymethylene polymer
WO2012129070A2 (fr) 2011-03-24 2012-09-27 Unversity Of Florida Research Foundation, Inc. Polymérisation par métathèse d'acétal
EP2505609B1 (fr) 2011-04-01 2015-01-21 Ticona GmbH Polyoxyméthylène avec une grande résistance aux chocs pour moulage par soufflage-extrusion
EP2546272A1 (fr) 2011-07-15 2013-01-16 Ticona GmbH Procédé de production de polymères d'oxyméthylène
US8968858B2 (en) 2011-12-30 2015-03-03 Ticona Llc Printable molded articles made from a polyoxymethylene polymer composition
EP2938674A1 (fr) 2012-12-27 2015-11-04 Ticona LLC Composition de polyoxyméthylène à résistance au choc modifiée et articles, fabriqués avec celle-ci, stables lors d'une exposition à une lumière ultraviolette
JP2016089069A (ja) * 2014-11-06 2016-05-23 旭化成ケミカルズ株式会社 ポリアセタール樹脂ペレット及び成形体
JP6623055B2 (ja) * 2015-12-15 2019-12-18 旭化成株式会社 ポリアセタールの製造方法

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US3027352A (en) 1958-02-28 1962-03-27 Celanese Corp Copolymers
DE1161421B (de) 1961-05-06 1964-01-16 Hoechst Ag Verfahren zur kontinuierlichen Polymerisation von Trioxan oder zur Mischpolymerisation von Trioxan mit anderen Comonomeren
DE1495228A1 (de) 1961-04-05 1969-02-13 Celanese Corp Verfahren zur direkten Herstellung von pulverfoermigen Oxymethylenpolymeren
DE1720358A1 (de) 1966-01-07 1972-04-13 Celanese Corp Verfahren und Vorrichtung zur direkten Herstellung von pulverfoermigen Oxymethylenpolymeren
US3803094A (en) 1972-07-12 1974-04-09 Ube Industries Process for producing formaldehyde copolymer
DE3018898C2 (fr) 1979-05-18 1993-02-11 Mitsubishi Gas Chemical Co., Inc., Tokio/Tokyo, Jp
EP0347119B1 (fr) 1988-06-13 1993-12-08 Polyplastics Co. Ltd. Procédé de préparation de polymères ou copolymères d'acetal
EP0325052B1 (fr) 1987-12-25 1994-11-02 Polyplastics Co. Ltd. Procédé de préparation de polyacétales ou de copolyacétales
DE4327246A1 (de) 1993-08-13 1995-02-16 Hoechst Ag Vorrichtung zur kontinuierlichen Herstellung von Polyacetalen und ihre Verwendung
DE4327245A1 (de) 1993-08-13 1995-02-16 Hoechst Ag Verfahren zur Herstellung von Polyacetalen
DE4423617A1 (de) 1994-07-06 1996-01-11 Hoechst Ag Verfahren zur Herstellung von Polyacetalen

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DE2362791C2 (de) * 1973-12-18 1982-07-01 Hoechst Ag, 6000 Frankfurt Verfahren zur Herstellung von Copolymeren des Trioxans
DE2620017C3 (de) * 1976-05-06 1979-05-31 Hoechst Ag, 6000 Frankfurt Verfahren zur Herstellung von grobkörnigen Oxymethylenpolymeren
DE3147309A1 (de) * 1981-11-28 1983-06-01 Basf Ag, 6700 Ludwigshafen Kontinuierliches verfahren zur herstellung von oxymethylenpolymeren
DE3703790A1 (de) * 1987-02-07 1988-08-18 Hoechst Ag Kontinuierliches verfahren zur entfernung instabiler anteile aus rohem oxymethylencopolymerisat

Patent Citations (11)

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Publication number Priority date Publication date Assignee Title
US3027352A (en) 1958-02-28 1962-03-27 Celanese Corp Copolymers
DE1495228A1 (de) 1961-04-05 1969-02-13 Celanese Corp Verfahren zur direkten Herstellung von pulverfoermigen Oxymethylenpolymeren
DE1161421B (de) 1961-05-06 1964-01-16 Hoechst Ag Verfahren zur kontinuierlichen Polymerisation von Trioxan oder zur Mischpolymerisation von Trioxan mit anderen Comonomeren
DE1720358A1 (de) 1966-01-07 1972-04-13 Celanese Corp Verfahren und Vorrichtung zur direkten Herstellung von pulverfoermigen Oxymethylenpolymeren
US3803094A (en) 1972-07-12 1974-04-09 Ube Industries Process for producing formaldehyde copolymer
DE3018898C2 (fr) 1979-05-18 1993-02-11 Mitsubishi Gas Chemical Co., Inc., Tokio/Tokyo, Jp
EP0325052B1 (fr) 1987-12-25 1994-11-02 Polyplastics Co. Ltd. Procédé de préparation de polyacétales ou de copolyacétales
EP0347119B1 (fr) 1988-06-13 1993-12-08 Polyplastics Co. Ltd. Procédé de préparation de polymères ou copolymères d'acetal
DE4327246A1 (de) 1993-08-13 1995-02-16 Hoechst Ag Vorrichtung zur kontinuierlichen Herstellung von Polyacetalen und ihre Verwendung
DE4327245A1 (de) 1993-08-13 1995-02-16 Hoechst Ag Verfahren zur Herstellung von Polyacetalen
DE4423617A1 (de) 1994-07-06 1996-01-11 Hoechst Ag Verfahren zur Herstellung von Polyacetalen

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5886139A (en) * 1996-04-12 1999-03-23 Polyplastics Co., Ltd. Process for producing polyacetal copolymer
WO2006105970A1 (fr) * 2005-04-08 2006-10-12 Ticona Gmbh Procede pour produire des homopolymeres et des copolymeres de polyoxymethylene et dispositif associe
WO2006120218A1 (fr) * 2005-05-11 2006-11-16 Basf Aktiengesellschaft Procede ameliore d'extraction de monomeres residuels a partir de polyoxymethylenes
WO2013020830A2 (fr) 2011-08-11 2013-02-14 Basf Se Procédé de traitement de polyoxyméthylène brut particulaire
US8859721B2 (en) 2011-08-11 2014-10-14 Basf Se Process for working up particulate crude polyoxymethylene

Also Published As

Publication number Publication date
KR960010705A (ko) 1996-04-20
BR9503924A (pt) 1996-09-17
EP0699695B1 (fr) 2002-07-31
JP3369365B2 (ja) 2003-01-20
US5587449A (en) 1996-12-24
JPH0873549A (ja) 1996-03-19
EP0699695A3 (fr) 1997-10-01
DE59510299D1 (de) 2002-09-05
CN1131163A (zh) 1996-09-18
ES2180598T3 (es) 2003-02-16
KR100360288B1 (ko) 2003-01-24
CA2157456A1 (fr) 1996-03-06
DE4431575A1 (de) 1996-03-07
TW376392B (en) 1999-12-11

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